Dyes for color filters and photosensitive resist resin composition containing the same

ABSTRACT

Dyes suitable for use in the fabrication of color filters are described which contain one or more photopolymerizable substituents preferably represented by the following formula:D-(A-Yn1)n2(1)where D represents a chromophoric nucleus, A denotes a connecting group, Y means the photopolymerizable group, n1 is 1-10,000, and n2 stands for an integer of 1-10. Also described are photosensitive resist resin compositions containing the dyes as well as color filters fabricated by curing the photosensitive resist resin compositions.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation of application Ser. No. 08/653,252 filed on May24,1996, now U.S. Pat. No. 5,789,137, which is a divisional ofapplication Ser. No. 08/223,605 filed on Apr. 6, 1994, now U.S. Pat. No.5,578,419; which is a continuation-in-part of application Ser. No.07/987,960 filed on Dec. 11, 1992.

BACKGROUND OF THE INVENTION

1) Field of the Invention

This invention relates to dyes for color filters suitable for use inliquid crystal television sets, color image pickup tubes and colorcopying machines, photosensitive resist resin compositions containingthe dyes, and color filters fabricated by curing the resin compositions.

2) Related Art of the Invention

Known fabrication processes of color filters include printing processesutilizing the principle of printing, dyeing processes and pigmentprinting processes, both making use of photolithography, andelectrodeposition processes involving electrochemical deposition of adye ("Nikkei New Material", 48-56 (Feb. 25, 1991)).

Fabrication of a filter by a dyeing process comprises, as shown in FIG.1 by way of example, the following steps: (1) coating a glass substratewith a coating formulation which is formed of a water-soluble dyeablehigh-molecular material, such as gelatin or casein, and to which hasbeen imparted photosensitivity by the addition of a bichromate, (2)exposing the thus-formed coating to ultraviolet rays through aphotomask, (3) developing the thus-exposed coating to form a pattern,(4) coloring the pattern with an acid dye, (5) subjecting thethus-colored pattern to color-mixing protection, and (6) repeating steps(1) to (5) until the other two colors are applied to the glasssubstrate. The color filter obtained by the dyeing process has excellentpattern resolution and dimensional accuracy, superb light transmissionand high lightness. Such a dyeing process is, however, accompanied bythe following drawbacks:

(1) If the glass substrate is dyed with the second color withoutapplying color protection subsequent to its coloration with the firstcolor, the dye for the second color migrates into the filter layer ofthe first color so that the spectral characteristics are deteriorated.To avoid this problem, it is necessary to apply a color protection filmwith an acryl, urethane or epoxy resin or to subject the surface of thedyed medium to chemical treatment with tannic acid or the like.

(2) The heat resistance is insufficient due to the use of gelatin orcasein as the base of the photosensitive resin.

On the other hand, fabrication of a filter by a pigment printing processmakes use of a pigment which is employed for heat-resistant paints orfor the coloration of plastics, and as depicted in FIG. 2 by way ofexample, comprises the following steps: (1) coating a glass substratewith a photosensitive resin containing a pigment uniformly dispersedtherein, (2) exposing the thus-coated glass substrate to ultravioletrays, (3) developing the thus-exposed coating to form a colored pattern,and (4) repeating the steps (1) to (3) until the other two colors areapplied to the glass substrate. The color filter obtained by the pigmentprinting process has pattern accuracy as high as that obtained by thedyeing process and is also excellent in heat resistance and lightresistance, but is accompanied by the following drawbacks:

(1) Its light transmission is inferior and its contrast is low, becauselight is scattered by the pigment particles.

(2) Prior to coating the photosensitive resin in which the pigment isuniformly dispersed, the resin should be passed through a filter toeliminate dust and large particles. Processing troubles therefore occurincluding clogging of the filter by coagulated pigment particles.

If the process shown in FIG. 2 is followed to fabricate a filter byusing "M/P Pink REL" (trade name; product of Mitsui Toatsu Dyes, Ltd.)or "PS Green B" (trade name; product of Mitsui Toatsu Dyes, Ltd.), aresin-soluble conventional dye, instead of a pigment, the conventionaldye is not immobilized in a matrix because its molecular weight is lowerthan 500. As a consequence, the dye may move to an adjacent matrix andcause color mixing. Further, the solubility of the conventional dye isinsufficient so that the color filter must have a great film thicknessin order to obtain a desired color density.

It is conceivable to immobilize a dye in a matrix resin using, as thedye, a reactive dye containing a monochlorotriazinyl group or asulfatoethylsulfone group. Such reactive groups are however of the heatreactive type, thereby making it extremely difficult to fabricatemicro-matrices like color filters. In addition, a salt remains in theresin after the reaction so that the electrical insulating property isimpaired.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novel dye for a colorfilter, which is free of problems such as the above-mentioned filterclogging, requires no treatment for the prevention of mixing ofindividual colors and can furnish a color filter which has goodtransmission characteristics and is excellent in durability such as heatresistance, light resistance and moistureproofness.

Another object of the present invention is to provide a photosensitiveresist resin composition containing the above-described novel dye for acolor filter.

A further object of the present invention is to provide a color filterhaving good transmission characteristics and excellent durability suchas heat resistance, light resistance and moistureproofness.

To attain the above objects, the present inventors have proceeded withan extensive investigation. As a result, it has been found that a dyemeeting at least one of the below-described two requirements can bestably immobilized in a filter matrix and can hence provide a colorfilter free of dye color mixing and excellent in transmissioncharacteristics and durability. These requirements are:

(1) Possession of a photopolymerizable substituent; and

(2) Molecular weight of at least 500 but not greater than 4000.

Use of a dye capable of satisfying at least either one of theserequirements makes it possible to stably immobilize the dye in a filtermatrix.

The present invention therefore provides dyes represented by thebelow-described formula (1),

    D-(A-Y.sub.n.sup.1).sub.n.sup.2                            ( 1)

wherein D represents a chromophoric nucleus, A denotes a connectinggroup, Y means the photopolymerizable group, _(n) ¹ is 1-10000, and _(n)² stands for an integer of 1-10.

The present invention also provides dyes having a molecular weight of atleast 500 but not greater than 4000 and represented by thebelow-described formula (8) or (9),

    D-(B-Z).sub.m                                              ( 8)

    D-E-D                                                      (9)

wherein D in each formula represents a chromophoric nucleus, and B and Eeach denotes a connecting group, Z is --COOR⁹, CONR¹⁰ R¹¹, --OCOR¹²,--OCOOR¹³, --OCONHR¹⁴, --NHR¹⁵ or --NR¹⁶ R¹⁷, R⁹ and R¹² to R¹⁷independently representing a substituted or unsubstituted alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aryl group or a substituted or unsubstituted aralkyl groupand R¹⁰ and R¹¹ independently representing a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted aralkyl group or a hydrogen atom, and m stands for aninteger of 1-10.

The present invention also provides photosensitive resist resincompositions comprising the aforesaid dyes, and LCD color filtersfabricated by curing the photosensitive resist resin compositions.

The dyes according to the present invention are suitable as dyes forcolor filters for the following reasons:

(1) The dyes according to this invention are soluble in a resin.Especially, the dyes containing one or more ester, amido, acyl,carbamoyl, amino and/or like groups in their molecules have excellentcompatibility with a resin so that they do not develop clogging orcoating irregularities when they are coated upon fabrication of colorfilters having red, green and blue matrices with a photosensitive resistresin.

(2) The dyes according to this invention contain one or morephotopolymerizable substituents. Upon photo-setting a resist resincomposition, each dye and a photosensitive resist resin arecopolymerized or polymerization takes place between molecules of eachdye so that the dye is immobilized in the resin matrix. In the case ofeach dye having a high molecular weight of at least 500 but not greaterthan 4000, it does not migrate of a resin matrix once it enters theresin matrix and is incorporated therein. As a consequence, it ispossible to avoid color mixing that may otherwise take place due tomigration of the dye into an adjacent layer of a different color.

(3) As the dyes according to this invention are each immobilized in amatrix, the resulting color filter is free from discoloration which mayotherwise take place as a result of sublimation of the dye, and is alsoexcellent in durability such as heat resistance and moistureproofness.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-section showing fabrication steps of a colorfilter according to a conventional dyeing process;

FIG. 2 is a schematic cross-section illustrating fabrication steps of acolor filter according to a conventional pigment printing process; and

FIGS. 3 through 6 are cross-sections depicting fabrication steps of acolor filter according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "polymerizable substituents" as used herein means groupscapable of inducing copolymerization between a resin and a dye orbetween dyes under light as well as photosensitive groups used inphotosensitive resist resins disclosed in the literature (for example,"Photopolymer Handbook" compiled by Photo Polymer Association andpublished by Kogyo Chosakai, 1989). It includes those employed to bonddye molecules in a pendant-like form from resin molecules.

Preferred examples of dyes bonded thereon according to the presentinvention with photosensitive polymerizable substituents include thoserepresented by the formula (1). In addition, it is preferred that thephotosensitive group represented by Y in the formula (1) is selectedfrom the group consisting of the following formulas (2)-(7): ##STR1##wherein R¹ to R⁴ independently represent a substituted or unsubstitutedalkyl group, a substituted or unsubstituted cycloalkyl group, asubstituted or unsubstituted aralkyl group, or a hydrogen atom; R⁵represents a substituted or substituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, or a substituted or unsubstituted aralkyl group, or a hydrogenatom; R^(5') is a hydrogen atom or a methyl group, provided that ifR^(5') is a methyl group, then R⁵ is a hydrogen atom; and R⁶, R⁷ and R⁸independently represent a substituted or unsubstituted alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted alkoxy group, a halogen atom, or a hydrogen atom.

It is preferred that if Y is formula (4), then D is the quinophthalonenucleus, the anthraquinone nucleus represented by any one of formulae(i) to (III), (VII) and (VIII) or a phthalocyanine nucleus representedby formula (ix) ##STR2## wherein R'⁵⁸ is a substituted or unsubstitutedalkyl group,a substituted or unsubstituted aryl group or a substitutedor unsubstituted aralkyl group, Met is a divalent metal, a trivalentmono-substituted metal, a tetravalent di-substituted metal or a metaloxide, and Z is a hydrogen or halogen atom.

In the formulas (2) to (8), examples of the unsubstituted alkyl groupinclude linear and branched alkyl groups such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl,iso-pentyl, neo-pentyl, 1,2-dimethylpropyl, n-hexyl, n-dodecyl,2-methylbutyl, 2-methylpentyl, 1,3-dimethylbutyl, 1-iso-propylpropyl,1,2-dimethylbutyl, n-heptyl, 1,4-dimethylpentyl,2-methyl-1-iso-propylpropyl, 1-ethyl-3-methylbutyl, n-octyl;2-ethylhexyl, 2-methyl-1-iso-propylbutyl,2,2-dimethyl-1-iso-propyl-1-t-butylpropyl, and n-nonyl. Exemplarysubstituted alkyl groups include alkoxyalkyl groups such asmethoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl,γ-methoxypropyl, γ-ethoxypropyl, methoxyethoxyethyl, ethoxyethoxyethyl,dimethoxymethyl, diethoxymethyl, dimethoxyethyl, and diethoxyethyl;halogenated alkyl groups such as chloromethyl, 2,2,2-trichloroethyl,trifluoromethyl, and 1,1,1,3,3,3-hexafluoro-2-propyl; and hydroxyalkylgroups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl,hydroxypentyl, and hydroxyoctyl.

Examples of the unsubstituted cycloalkyl group include cyclopentyl andcyclohexyl. Exemplary substituted cycloalkyl groups include cyclopentyland cyclohexyl groups substituted by one or more groups, for example,alkyl groups such as methyl, ethyl and propyl, alkoxy groups such asmethoxy, ethoxy and butoxy, halogen atoms such as chlorine, bromine,fluorine and iodine, cyano groups, nitro groups and/or hydroxyl groups.

Examples of the unsubstituted alkoxyl group include methoxyl, ethoxyl,n-propoxyl, iso-propoxyl, n-butoxyl, iso-butoxyl, sec-butoxyl,t-butoxyl, n-pentoxyl, iso-pentoxyl, neo-pentoxyl, 1,2-dimethylpropoxyl,n-hexyloxyl, cyclohexyloxyl, 1,3-dimethylbutoxyl, 1-iso-propylpropoxyl,1,2-dimethylbutoxyl, n-heptyloxyl, 1,4-dimethylpentyloxyl,2-methyl-1-iso-propylpropoxyl, 1-ethyl-3-methylbutoxyl, n-octyloxyl,2-ethylhexyloxyl, 3-methyl-1-iso-propylbutoxyl,2-methyl-1-iso-propylbutoxyl, 1-t-butyl-2-methylpropoxyl, n-nonyloxyland n-decyloxyl. Exemplary substituted alkoxyl groups includealkoxyalkoxyl groups such as methoxymethoxyl, methoxyethoxyl,ethoxyethoxyl, propoxyethoxyl, butoxyethoxyl, γ-methoxypropoxyl,γ-ethoxypropoxyl, methoxyethoxyethoxyl, ethoxyethoxyethoxyl,dimethoxymethoxyl, diethoxymethoxyl, dimethoxyethoxyl, anddiethoxyethoxyl; halogenated alkoxyl groups such as chloromethoxyl,2,2,2-trichloroethoxyl, trifluoromethoxyl, and1,1,1,3,3,3-hexafluoro-2-propoxyl; and hydroxyalkoxyl groups such ashydroxymethoxyl, hydroxyethoxyl, hydroxypropoxyl, hydroxybutoxyl,hydroxypentyloxyl, and hydroxyoctyloxyl.

Illustrative of the unsubstituted aryl group include phenyl, naphthyland indenyl.

Examples of the substituted aryl group include phenyl, naphthyl andindenyl groups containing one or more substituents, for example, linearand branched alkyl groups such as methyl, ethyl, propyl, iso-propyl,butyl, 2-methylpropyl, pentyl and/or neo-pentyl, alkoxyl groups such asmethoxyl, ethoxyl and/or propoxyl and/or halogen atoms such as chlorine,fluorine, bromine-and/or iodine.

Examples of the unsubstituted aralkyl group include benzyl andphenethyl.

Illustrative of the substituted aralkyl group include benzyl andphenethyl groups containing one or more substituents, for example,linear and branched alkyl groups such as methyl, ethyl, propyl,iso-propyl, butyl, 2-methylpropyl, pentyl and/or neo-pentyl, alkoxylgroups such as methoxyl, ethoxyl and/or propoxyl, and/or halogen atomssuch as chlorine, fluorine, bromine and/or iodine.

Exemplary halogen atoms include chlorine, bromine, iodine and fluorine.

In the formulas (1), (8) and (9), any known skeletons disclosed inliterature can be used as the chromophoric nucleus represented by D,including azo, anthraquinone, phthalocyanine, quinophthalone styrylic,indoaniline and cyanine skeletons (see, for example, "Color Handbook",compiled by Ohkawara et al., Kodansha Ltd. (1986), "The Chemistry ofSynthetic Dyes", Vols. I-VI, edited by K. Venkataraman et al. andpublished by Academic Press, and "synthetic Dye Overview" written byHiroshi Horiguchi, Sankyo Publishing Co.". The skeletons willhereinafter be described specifically. They can contain one or moresubstituents thereon. Each connecting group in the formulas (1), (8) and(9) can bond to a substituent which has been bonded to a chromophoricnucleus. ##STR3##

Particularly preferred, illustrative chromophoric nuclei include, fromthe viewpoint of durability, dye skeletons represented by the followingformulas (16) to (18): ##STR4## wherein Y¹ represents 1-15 same ordifferent substituents selected from hydrogen atoms, substituted andunsubstituted alkyl groups, substituted and unsubstituted cycloalkylgroups, substituted and unsubstituted aryl groups, substituted orunsubstituted alkoxyl groups, substituted and unsubstituted aryloxylgroups, substituted and unsubstituted alkylthio groups, substituted andunsubstituted arylthio groups, substituted and unsubstituted alkylaminogroups, substituted and unsubstituted dialkylamino groups, substitutedand unsubstituted arylamino groups, substituted and unsubstituteddiarylamino groups, amino groups, halogen atoms, nitro group, nitrilegroup, substituted and unsubstituted acyl groups, substituted andunsubstituted alkoxycarbonyl groups, and substituted and unsubstitutedamido groups; Met is a divalent metal, a trivalent mono-substitutedmetal, a tetravalent di-substituted metal, or a metal oxide; and lstands for an integer from 1-15; ##STR5## wherein Y² represents 1-7 sameor different substituents selected from hydrogen atoms, substituted andunsubstituted alkyl groups, substituted and unsubstituted cycloalkylgroups, substituted and unsubstituted aryl groups, substituted andunsubstituted alkoxyl groups, substituted and unsubstituted aryloxylgroups, substituted and unsubstituted alkylthio groups, substituted andunsubstituted arylthio groups, substituted and unsubstituted alkylaminogroups, substituted and unsubstituted dialkylamino groups, substitutedand unsubstituted arylamino groups, substituted and unsubstituteddiarylamino groups, hydroxy group, amino groups, halogen atoms, nitrogroup, nitrile group, substituted or unsubstituted acyl groups,substituted and unsubstituted alkoxycarbonyl groups, substituted orunsubstituted 2,3-dicarboxyimide groups, and substituted andunsubstituted amido groups; and p stands for an integer of from 1-7;##STR6## wherein Y³ represents 1-8 same or different substituentsselected from hydrogen atoms, substituted and unsubstituted alkylgroups, substituted and unsubstituted cycloalkyl groups, substituted andunsubstituted aryl groups, substituted and unsubstituted alkoxyl groups,substituted and unsubstituted aryloxyl groups, substituted andunsubstituted alkylthio groups, substituted and unsubstituted arylthiogroups, substituted and unsubstituted alkylamino groups, substituted andunsubstituted dialkylamino groups, substituted and unsubstitutedarylamino, substituted and unsubstituted diarylamino groups, aminogroups, halogen atoms, nitro group, nitrile group, substituted andunsubstituted acyl groups, substituted and unsubstituted alkoxycarbonylgroups, and substituted and unsubstituted amido groups; and q stands foran integer of from 1-8.

Also preferred for the group D of formulae (1), (8) and (9) are groupsof the formula (i), (ii), (iii), (vii) and (viii) described as follows:##STR7## wherein X is an oxygen or sulfur atom, R'¹ to R'⁴ each areindependently a hydrogen atom, a substituted or unsubstituted alkylgroup, a substituted or unsubstituted alkoxy group or a halogen atom;##STR8## wherein X is an oxygen or sulfur atom, R'⁵ to R'⁸ each areindependently a substituted or unsubstituted alkyl group, a substitutedor unsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup or a hydrogen atom, R'⁹ to R'¹² each are independently a hydrogenatom, substituted or unsubstituted alkyl group, a substituted orunsubstituted alkoxy group or a halogen atom; ##STR9## wherein X is anoxygen or sulfur atom, R'¹³ to R'¹⁸ each are independently a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted alkoxy group or a halogen atom, R'¹⁹ to R'²² each areindependently a substituted or unsubstituted cycloalkyl group, asubstituted or unsubstituted aryl group or a hydrogen atom; ##STR10##wherein R'⁴⁷ to R'⁵⁴ each are independently a hydrogen atom, asubstituted or unsubstituted alkyl group, substituted or unsubstitutedalkoxy group, a substituted or unsubstituted cycloalkyl group or ahalogen atom, R'⁵⁵ and R'⁵⁶ each are independently a substituted orunsubstituted alkyl group, a substituted or unsubstituted alkoxy group,a cyano group, a halogen atom or a hydrogen atom; ##STR11## wherein R'⁵⁷is a substituted or unsubstituted alkyl group or a substituted orunsubstituted aryl group.

In formula (1), the connecting group represented by A can be anyconnecting group which can covalently bond a chromophoric nucleus or itssubstituent to photopolymerizable group Y. Alternatively, it is possibleto directly bond a chromophoric nucleus or its substituent tophotopolymerizable group Y without the connecting group A. Examples ofthe connecting group A include those represented by the followingformulas (19) to (22), in which parenthesized recurring units may becombined together at random: ##STR12## wherein one of R²⁶ and R²⁷represents a hydrogen atom and the other denotes a hydroxyl group; andr¹ and s¹ each stands for an integer of from 1-10000; ##STR13## whereinR²⁸ to R³¹ independently represent a hydrogen atom, a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted aryl group, or a halogen atom; andr² stands for an integer of from 1-10000; ##STR14## wherein r³ standsfor an integer of 1-10000. ##STR15## wherein R³² to R³⁷ independentlyrepresent a hydrogen atom, a halogen atom, a hydroxyl group, --SH, anamino group, a substituted or unsubstituted alkyl group, a substitutedor unsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted alkoxyl group, a substituted orunsubstituted aryloxyl group, a substituted or unsubstituted alkylaminogroup, or a substituted or unsubstituted arylamino group; and a¹, b¹ andc¹ each stands for an integer of from 0-10000.

The connecting group represented by B in the formula (8) can be anydivalent connecting group. Alternatively, it is possible to directlybond a chromophoric nucleus to a substituent without the connectinggroup B. Its examples include the groups represented by formulas (20) to(22) in which r¹ to r³, s¹, a¹, b¹ and c¹ each stands for an integer offrom 1-100. The connecting group represented by E in the formula (9) canbe any divalent connecting group. Its examples include--F--OCO--G--COO--F--, --F--COO--G--OOC--F--, --F--CONH--G--NHCO--F--,--F--OCONH--G--NHCOO--F-- and --F--OCOO-G--OCOO--F--. F and G can be anydivalent connecting groups. Their examples include the groupsrepresented by the formulas (20) to (23) in which r¹ to r³, s¹, a¹, b¹and c¹ each stands for an integer of from 1-100, and parenthesizedrecurring units may be combined together at random.

Formula (23) connecting groups are those of the formula ##STR16##wherein R³⁸ to R⁴⁹ independently represent a hydrogen atom, asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedcycloalkyl group, a substituted or unsubstituted aryl group, or ahalogen atom; R⁵⁰ and R⁵¹ independently represent a hydrogen atom, asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedcycloalkyl group, a substituted or unsubstituted aryl group, asubstituted or unsubstituted alkoxyl group, or a halogen atom; a², b²,c², a³, b³ and c³ each stands for an integer of from 0-100; and d standsfor an integer of 1-5.

Each photosensitive resist resin composition according to the presentinvention comprises at least one of the dyes of the present inventionand a resist resin containing photosensitive groups therein. It mayfurther contain a photopolymerization initiator, a diluent, and one ormore other additives.

The dyes represented by the formula (1) or (8) can each be synthesizedby one of the following processes:

(1) a process in which the connecting group is bonded to thechromophoric nucleus D, followed by bonding of Y or Z;

(2) a process in which the connecting group is bonded to Y or Z,followed by bonding to the chromophoric nucleus D;

(3) a process in which a chromophoric nucleus intermediate is reacted tothe connecting group or with a connecting group containing Y or Z,followed by the construction of the corresponding chromophoric nucleus.One of these processes can be selected suitably depending on thecombination of the chromophoric nucleus D, the connecting group and thegroup Y or Z;

The dyes represented by the formula (9) can each be synthesized by oneof the following processes:

(1) a process in which the chromophoric nucleus D is reacted with theconnecting group E, which contains a bifunctional group, in an amount of0.5 equivalent or less to conduct dimerization;

(2) a process in which the connecting group E is bonded to thechromophoric nucleus D, followed by the bonding of the chromophoricnucleus D. One of these processes can be selected suitably depending onthe combination of the chromophoric nucleus D and the connecting groupE;

In the process of the present invention for the fabrication of a colorfilter, any photosensitive resist resin can be used in combination withthe dye of the present invention as long as the resin is curable bylight. Namely, any resin containing one or more photosensitive groupsand which is know in the literature can be used (see "RecordingMaterials and Photosensitive Resins", published by the PublicationCenter of the Japan Society for the Promotion of Science; and"Photopolymer Handbook", compiled by Photopolymer Association andpublished by Kogyo Chosakai, 1989). Preferred are resist resinscontaining photosensitive groups selected from the group consisting ofthe following formulas (10) to (15): ##STR17## wherein R¹⁸ to R²¹independently represent a substituted or unsubstituted alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aralkyl group, or a hydrogen atom; R²² represents asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedcycloalkyl group, a substituted or unsubstituted aryl group, asubstituted or unsubstituted aralkyl group, or a hydrogen atom; and R²³to R²⁵ independently represent a substituted or unsubstituted alkylgroup, a substituted or unsubstituted cycloalkyl group, a substituted orunsubstituted alkoxyl group, a hydrogen atom, or a halogen atom.

The color filter of the present invention can be fabricated, as oneexample, by dissolving beforehand the dye of the present invention (red,green or blue) in a photosensitive resin composition, forming theresulting formulation into a film on a substrate by casting, spincoating or the like and then patterning the film by exposure to light.Alternatively, at least two kinds of dyes of the present invention canbe mixed to obtain a red, green or blue color.

With reference to the accompanying drawings, a typical filterfabrication process will hereinafter be described taking the fabricationof a stripe filter as one example.

First, one of the dyes (red, green or blue) according to this inventionis dissolved in a solvent containing photosensitive resin at aproportion of 1-100 parts by weight, preferably 40-100 parts by weightin 100 parts by weight of a photosensitive resin, and the resultingformulation is spin-coated on a substrate 1 by using a spinner (FIG. 3).The thickness of a resist layer 2 is usually 0.5-100 μm although it isdetermined depending on spectroscopic characteristics desired. After theresist layer 2 is dried, the resist layer 2 is pre-baked under suitabletemperature conditions. The resist layer is exposed to light or anelectron beam, to which the resist has sensitivity, through a mask 3having a desired pattern corresponding to a pattern to be formed (e.g.,a stripe pattern)--FIG. 4. The resist layer so exposed is then developedto form a pattern 4 (FIG. 5). Finally, post-baking is applied underappropriate temperature conditions.

To form a color filter having two or more colors, the steps of from FIG.3 to FIG. 5 are repeated using dyes corresponding to the respectivecolors as needed, namely, as many times as the number of filter colorsemployed, thereby making it possible to form, for example, a colorfilter having three colored layers 5,6,7 of different colors as shown inFIG. 6. Where a black matrix is formed, it is desired to form it beforethe formation of colored layers.

As has been described above, patterning of each dye layer can beconducted on an optically transparent substrate. No particularlimitation is imposed on the substrate to be used, insofar as it permitspatterning of the dye layer and the color filter so formed functions asdesired.

Examples of the substrate include a glass plate; and films or plates ofresins such as polyvinyl alcohol, hydroxyethylcellulose, polymethylmethacrylate, polyesters, polybutyral, polyamides, polyethylene,polyvinyl chloride, polyvinylidene chloride, polycarbonates, polyolefincopolymers, vinyl chloride copolymers, vinylidene chloride copolymersand styrene copolymers. A patterned dye layer can be formed integrallywith a substrate which is applied as a color filter.

The present invention will hereinafter be described in detail by thefollowing examples. It should however be borne in mind that thisinvention should not be limited to or by the following examples.

EXAMPLE 1

A mixture of ten parts of 1-amino-4-hydroxy-2-chloroanthraquinone, 5parts of polyvinyl alcohol having an average molecular weight of 750, 5parts of potassium carbonate and 100 parts of dimethylformamide washeated to 120° C. and then, reacted for 10 hours. The reaction mixturewas poured into 500 parts of 5% hydrochloric acid solution, followed byextraction with 100 parts of chloroform. The extract was purified bycolumn chromatography (eluent: chloroform-methanol). The purifiedproduct (8 parts) and the compound represented by the following formula(24): ##STR18## were then reacted. The reaction product was purified bycolumn chromatography, whereby 7 parts of the compound represented bythe following formula (25): ##STR19## and its isomer were obtained.

EXAMPLE 2

A mixture of 14 parts of 3-nitrophthalonitrile, 10 parts of polyvinylalcohol having an average molecular weight of 750, 5 parts of sodiumhydride and 200 parts of dimethylformamide was heated to 120° C. andthen, reacted for 10 hours. The reaction mixture was extracted with 500parts of chloroform. The extract was purified by column chromatography(eluent: chloroform-methanol). The purified product (5 parts), 1 part ofcuprous chloride, 4 parts of diazabicycloundecene and 100 parts ofn-amyl alcohol were mixed, followed by reaction for 6 hours underreflux. The reaction mixture was concentrated under reduced pressure todistill off the amyl alcohol. The residue was purified by columnchromatography. The purified product (7 parts) and the compoundrepresented by the formula (24) were then reacted. The reaction productwas purified by column chromatography, whereby 7 parts of the compoundrepresented by the following formula (26): ##STR20## and its isomer wereobtained.

EXAMPLE 3

A mixture of ten parts of 1,4-diamino-2,3-dichloroanthraquinone, 5 partsof polyvinyl alcohol having an average molecular weight of 750, 5 partsof potassium carbonate and 50 parts of dimethylformamide was heated to120° C. and then, reacted for 10 hours. The reaction mixture was pouredinto 500 parts of 5% hydrochloric acid solution, followed by extractionwith 300 parts of chloroform. The extract was purified by columnchromatography (eluent: chloroform-methanol). The purified product (5parts) and the compound represented by the formula (24) were thenreacted. The reaction product was purified by column chromatography,whereby 5 parts of the compound represented by the following formula(27): ##STR21## and its isomer were obtained.

EXAMPLE 4

The dye (3.2 parts) of the formula (25) and 80 parts of a 20% solutionof a stilbazole photosensitive resin in polyvinyl alcohol were mixed. Acolor filter substrate with black stripes of 20 μm wide was spin-coatedto a thickness of 3 μm with the resulting mixture. After beingphotomasked, the substrate was exposed to ultraviolet rays under ahalogen lamp. The uncured parts were washed off, whereby a red filterlayer was formed. In a similar manner, a green and blue filter layerswere formed on the same substrate using dyes represented by the formulas(26) and (27), respectively.

The thus-obtained filter for a color LCD was free of color mixingbetween the individual colors and hence had vivid color tones. Inaddition, no quality deterioration was observed although it was heatedto 250° C. during formation of ITO electrodes. The filter did notundergo deterioration either in a weathering test by a weatherometer orin a light-resistance test under carbon arc lamps.

Comparative Example 1

In a similar manner to Example 4, a color filter was fabricated using"M/P Pink REL" and "PS Green B" (each, trade name; product of MitsuiToatsu Dyes, Ltd.) and "Macrolex Blue 2R" (trade name; product of BayerA.G.). In Table 1, characteristics of the color filter are presented incomparison with those of the color filter fabricated in Example 4.

The following methods and standards were followed for the measurementsof the respective characteristics and for the evaluation of themeasurement results.

1. Transmittance characteristics

A: Maximum transmittance ≧80%, with the proviso that the transmittanceis 10% or lower at (the wavelength for the maximum transmittance ±50nm).

C: Maximum transmittance ≦70%, with the proviso that the transmittanceis 10% or lower at (the wavelength for the maximum transmittance ±50)nm.

B: Other than A or C

2. Moistureproofness

Color difference was determined after each filter was stored at 95% R.H.and 60° C. for 200 hours.

A: ΔE≦3

B: 3<ΔE<5

C: ΔE≧5

3. Light resistance

Color difference was determined after each filter was exposed to lightwith a fadeometer at 60° C. for 200 hours.

A: ΔE≦3

B: 3<ΔE<5

C: ΔE≧5

4. Heat resistance

Color difference was determined after each filter was stored at 250° C.for 1 hour.

A: ΔE≦3

B: 3<ΔE<5

C: ΔE≧5

                  TABLE 1                                                         ______________________________________                                                        Example 4 Comp. Ex. 1                                         Migration of dye                                                                              Not observed                                                                            Observed                                            ______________________________________                                        Transmittance                                                                 characteristics                                                               Red             A         B                                                   Green           A         B                                                   Blue            A         C                                                   Moistureproofness                                                             Red             A         C                                                   Green           A         B                                                   Blue            A         C                                                   Light resistance                                                              Red             A         B                                                   Green           A         B                                                   Blue            A         C                                                   Heat resistance                                                               Red             A         C                                                   Green           A         B                                                   Blue            A         C                                                   ______________________________________                                    

EXAMPLE 5

Dissolved in 30 parts of glacial acetic acid were 10 parts of1-amino-2-p-acetylphenoxy-4-hydroxyanthraquinone and 3.5 parts ofbenzaldehyde. Sulfuric acid (2 parts) was added to the resultingsolution, followed by reaction at 40-45° C. for 12 hours. The reactionmixture was poured into 500 ml of water. The resulting precipitate wascollected by filtration, followed by drying. The residue was purified bycolumn chromatography, whereby 7 parts of the compound represented bythe following formula (28) were obtained.

                                      TABLE 2                                     __________________________________________________________________________     ##STR22##                                                                    1                                  (28)                                       λmax = 510 nm                                                          εg = 2.8 × 10.sup.4 ml/g · cm (solvent: toluene)       Elemental analysis for: C.sub.29 H.sub.19 NO.sub.5                                       C        H        N                                                __________________________________________________________________________    Calculated (%)                                                                           75.49    4.12     3.04                                             Found (%)  75.48    4.13     3.06                                             __________________________________________________________________________

EXAMPLE 6

Ten parts of 3-nitrophthalonitrile, 9.4 parts of p-hydroxyacetophenoneand 2.2 parts of 60% sodium hydride were added to 150 parts ofdimethylformamide and heated to 120° C., followed by reaction for 10hours. The reaction mixture was poured into 1000 parts of 5%hydrochloric acid solution, followed by extraction with 400 parts ofchloroform. The resulting extract was purified by column chromatography(eluent: chloroform-methanol). The compound so purified (5 parts), 0.5part of cuprous chloride, 2.7 parts of diazabicycloundecene and 50 partsof n-amyl alcohol were mixed, followed by reaction for 5 hours underreflux. Amyl alcohol was distilled off under reduced pressure from thereaction mixture, followed by purification by column chromatography.Three parts of the purified product and 0.4 part of benzaldehyde werereacted at 40-45° C. for 10 hours in 50 parts of glacial acetic acid inthe presence of sulfuric acid. The reaction mixture was poured into 500parts of water. The resulting mixture was filtered, dried and thenpurified by column chromatography, whereby 2 parts of the compoundrepresented by the following formula (29): ##STR23## and its isomer wereobtained.

Elemental analysis for C₉₂ H₅₆ N₈ O₈ Cu

                  TABLE 3                                                         ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            75.43        3.83   7.65                                          Found (%)   75.42        3.85   7.63                                          ______________________________________                                    

EXAMPLE 7

A mixture of ten parts of 1,4-diamino-2-chloroantraquinone, 7.5 parts ofp-mercaptoacetophenone, 1.2 parts of potassium carbonate and 50 parts ofdimethylformamide was heated to 120° C., followed by reaction for 10hours. The reaction mixture was poured into 500 parts of 5% hydrochloricacid solution, followed by extraction with 300 parts of chloroform. Theextract was purified by column chromatography (eluent:chloroform-methanol). Eight parts of the purified product and 2.8 partsof benzaldehyde were reacted at 40-45° C. for 9 hours in 60 parts ofglacial acetic acid in the presence of sulfuric acid. The reactionmixture was poured into 500 parts of water. The resulting precipitatewas filtered, dried and then purified by column chromatography, whereby6 parts of the compound represented by the following formula (30):##STR24## λmax=559 nm εg=3.4×10⁴ ml/g.cm (solvent: toluene)

Elemental analysis for C₂₉ H₂₀ N₂ O₃ S

                  TABLE 4                                                         ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            73.11        4.20   5.88                                          Found (%)   73.12        4.22   5.87                                          ______________________________________                                    

EXAMPLE 8

The dye (3.2 parts) of formula (28) and 80 parts of a 20% solution ofthe photosensitive resin disclosed in Japanese Patent Publication No.15026/1975 were mixed. A color filter substrate with black stripes of 20μm wide was spin-coated to a thickness of 3 μm with the resultingmixture. After being photomasked, the substrate was exposed toultraviolet rays under a halogen lamp. The uncured parts were washedoff, whereby a red filter layer was formed. In a similar manner, a greenand blue filter layers were formed using dyes represented by formula(29) and (30), respectively.

The thus-obtained filter for a color LCD was free of color mixingbetween the individual colors and hence had vivid color tones. Inaddition, no quality deterioration was observed although it was heatedto 250° C. during formation of ITO electrodes. The filter did notundergo deterioration either in a weathering test by a weatherometer orin a light-resistance test under carbon arc lamps.

EXAMPLE 9

Fifteen parts of 1-amino-4-hydroxy-2-p-methyl-phenoxyanthraquinone, 10parts of N-chloromethyl-α-phenylmaleimide and 3 parts of zinc chloridewere added to 80 parts of dichloroethane, followed by heating underreflux for 7 hours while shielding the reaction system from light andmoisture. The reaction mixture was cooled and then poured into 1000parts of methanol. The precipitated solid was collected by filtrationand then dried, whereby 7 parts of the compound represented by thefollowing formula (31): ##STR25## λmax=512 nm εg=2.5×10⁴ ml/g.cm(solvent: toluene) were obtained.

Elemental analysis for C₃₂ H₂₂ N₂ O₆ :

                  TABLE 5                                                         ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            72.45        4.15   5.28                                          Found (%)   72.43        4.20   5.29                                          ______________________________________                                    

EXAMPLE 10

After 15 parts of 1,4-diamino-2-p-hydroxyethyl-phenylthioanthraquinonewere converted to the sodium oxide with sodium hydride, it was reactedat 70° C. for 4 hours in a mixture consisting of 4.5 parts of acrylicchloride and 50 parts of pyridine. The reaction mixture was poured into500 parts of water. The precipitated solid was collected by filtrationand then dried. By chromatographic purification on a column, wereobtained 10 parts of the compound represented by the following formula(32): ##STR26## λmax=560 nm εg=3.2×10⁴ ml/g.cm (solvent: toluene)

Elemental analysis for C₂₅ H₂₀ N₂ O₄ S:

                  TABLE 6                                                         ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            67.57        4.51   6.31                                          Found (%)   67.59        4.55   6.33                                          ______________________________________                                    

EXAMPLE 11

Twenty parts of 1-amino-2-p-hydroxyethylphenoxy-4-hydroxyanthraquinonewere dissolved in 60 parts of pyridine, followed by the dropwiseaddition of 11 parts of benzenesulfonyl chloride at 5° C. After theywere reacted at 0-5° C. for 20 hours, the reaction mixture was pouredinto 1000 parts of water. The precipitated solid was collected byfiltration and dried, whereby 22 parts of a sulfonate ester wereobtained. The sulfonate ester (20 parts) was added to 80 parts ofpicoline, followed by reaction at 85° C. for 6 hours. The reactionmixture was concentrated in an evaporator so that 25 parts of thequaternary ammonium salt were obtained.

Twenty parts of the quaternary ammonium salt thus obtained, 4 parts ofbenzaldehyde and 7 parts of piperidine were added to 50 parts ofmethanol, followed by reaction at 45° C. for 200 hours under shade. Thereaction mixture was added dropwise to 1000 parts of diethyl ether toprecipitate a solid. The solid was collected by filtration and thendried, whereby 18 parts of the compound represented by the followingformula (33) were obtained: ##STR27## λmax=510 nm εg=2.2×10⁴ ml/g.cm(solvent: N,N-dimethylformamide)

Elemental analysis for C₄₁ H₃₂ N₂ O₇ S

                  TABLE 7                                                         ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            70.69        4.60   4.02                                          Found (%)   70.70        4.65   4.08                                          ______________________________________                                    

EXAMPLES 12-49

The compounds (D-A-Y) shown in Table 8 were synthesized likewise. Eachof color filters fabricated by using the compounds shown in Table 8 wasfree from color mixing between the colors and had vivid color tone. Inaddition, no quality deterioration was observed although they wereheated to 250° C. during formation of ITO electrodes. Those filter didnot undergo deterioration either in a weathering test by a weatherometeror in a light-resistance test under carbon arc lamps. Incidentally, eachλ_(max) was measured in N,N-dimethyl formamide.

    TABLE 8      - D.paren      open-st.A--Yn.sup.1)n.sup.2 (1)                                Compd.     No. D A Y n.sup.1 n.sup.2 λmax (nm)      34      ##STR28##     2  --(CH.sub.2 .paren      close-st..sub.2     ##STR29##     0  1 1 511     35      ##STR30##     2  --(CH.sub.2 .paren      close-st..sub.2     ##STR31##     1  1 1 510     36      ##STR32##     3  --(CH.sub.2 .paren      close-st..sub.2     ##STR33##     2  1 1 515     37      ##STR34##     2  None      ##STR35##     3  1 1 511     38      ##STR36##     4  None      ##STR37##     4  1 1 530     39      ##STR38##     5  --(CH.sub.2 .paren      close-st..sub.2     ##STR39##     2  1 1 528     40      ##STR40##     1      ##STR41##      ##STR42##     7  1 1 510     41      ##STR43##     6  --CH.sub.2      --     ##STR44##     4  1 1 508     42      ##STR45##     7  --CH.sub.2      --     ##STR46##     5  1 1 509     43      ##STR47##     2  None      ##STR48##     6  1 1 558     44      ##STR49##     2  None      ##STR50##     7  1 1 560     45      ##STR51##     2  None      ##STR52##     8  1 1 559     46      ##STR53##     8  --CH.sub.2      --     ##STR54##     9  1 1 561     47      ##STR55##     3  None      ##STR56##     0  1 1 550     48      ##STR57##     9  None      ##STR58##     1  1 2 550     49      ##STR59##     3  --CH.sub.2      --     ##STR60##     2  1 1 551     50      ##STR61##     3  --(CH.sub.2 .paren      close-st..sub.2     ##STR62##     3  1 1 550     51      ##STR63##     9  --(CH.sub.2 .paren      close-st..sub.2     ##STR64##     3  1 2 551     52      ##STR65##     0  None      ##STR66##     4  1 2 575     53      ##STR67##     1  --O--      ##STR68##     5  1 4 697     54      ##STR69##     2  --CH.sub.2      --     ##STR70##     6  1 4 699     55      ##STR71##     3      ##STR72##      ##STR73##     7  1 4 698     56      ##STR74##     4  --CH.sub.2      --     ##STR75##     8  1 4 720     57      ##STR76##     5  --CH.sub.2      --     ##STR77##     9  1 4 720     58      ##STR78##     6  --CH.sub.2      --     ##STR79##     0  1 4 685     59      ##STR80##     7  --CH.sub.2      --     ##STR81##     1  1 4 710     60      ##STR82##     8  None      ##STR83##     2  1 1 448     61      ##STR84##     9  --CH.sub.2      --     ##STR85##     3  1 1 450     62      ##STR86##     0  --CH.sub.2      --     ##STR87##     4  1 1 451     63      ##STR88##     1  None      ##STR89##     5  1 1 447     64      ##STR90##     2  None      ##STR91##     6  1 1 451     65      ##STR92##     3  --CH.sub.2      --     ##STR93##     7  1 2 663     66      ##STR94##     4  None      ##STR95##     8  1 2 680     67      ##STR96##     5  --CH.sub.2      --     ##STR97##     9  1 1 580     68      ##STR98##     6  None      ##STR99##     0  1 1 460     69      ##STR100##     7  --CH.sub.2      --     ##STR101##     1  1 1 585     70      ##STR102##     8  None      ##STR103##     2  1 1 583     71      ##STR104##     9  --CH.sub.2      --     ##STR105##     3  1 1 584

EXAMPLE 50

After 20 parts of 1,4-diamino-2-p-hydroxyphenyl-thioanthraquinone wereconverted to the sodium oxide with sodium hydride, it was reacted at 70°C. for 3 hours in a mixture consisting of 5.5 parts of terephthaloyldichloride and 90 parts of pyridine. The reaction mixture was pouredinto 500 parts of an aqueous methanol solution. The precipitated solidwas collected by filtration and then dried. By chromatographicpurification on a column, were obtained 13 parts of the compoundrepresented by the following formula (72): ##STR106## λmax=560 nmεg=3.1×10⁴ ml/g.cm (solvent: toluene)

Elemental analysis for C₄₈ H₃₀ N₄ O₈ S₂ (Mw: 854)

                  TABLE 9                                                         ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            67.45        3.51   6.56                                          Found (%)   67.48        3.59   6.53                                          ______________________________________                                    

EXAMPLE 51

After 20 parts of 1-amino-2-p-hydroxyethylphenoxy-4-hydroxyanthraquinonewere converted to the sodium oxide with sodium hydride, it was reactedat 70° C. for 3 hours in a mixture consisting of 4.9 parts ofterephthaloyl dichloride and 90 parts of pyridine. The reaction mixturewas poured into 500 parts of an aqueous methanol solution. Theprecipitated solid was collected by filtration and then dried. Bychromatographic purification on a column, were obtained 8 parts of thecompound represented by the following formula (73); ##STR107## λmax=509nm εg=1.8×10⁴ ml/g.cm (solvent: toluene)

Elemental analysis for C₅₂ H₃₆ N₂ O₁₂ (Mw: 880)

                  TABLE 10                                                        ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            70.91        4.09   3.18                                          Found (%)   70.95        4.18   3.16                                          ______________________________________                                    

EXAMPLE 52

Ten parts of 3-nitrophthalonitrile, 18 parts of ethylene glycol and 2.3parts of 60% sodium hydride were added to 150 parts of dimethylformamideand heated to 120° C., followed by reaction for 10 hours. The reactionmixture was poured into 1000 parts of 5% hydrochloric acid solution,followed by extraction with 400 parts of chloroform. The resultingextract was purified by column chromatography (eluent:chloroform-methanol). The compound so purified (5 parts), 0.7 part ofcuprous chloride, 4 parts of diazabicycloundecene and 50 parts of n-amylalcohol were mixed, followed by reaction for 5 hours under reflux. Amylalcohol was distilled off under reduced pressure from the reactionmixture, followed by purification by column chromatography. Three partsof the purified product and 2.3 part of benzoic chloride were reacted at70° C. for 3 hours in 30 parts of pyridine. The reaction mixture waspoured into 500 parts of water. The resulting precipitate was collectedby filtration, dried and then purified by column chromatography, whereby2.5 parts of the compound represented by the following formula (74) wereobtained: ##STR108## λmax=699 nm εg=2.1×10⁵ of a ml/g.cm (solvent:toluene)

Elemental analysis for C₆₈ H₄₈ N₈ O₁₂ Cu (Mw: 864)

                  TABLE 11                                                        ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            66.26        3.90   9.09                                          Found (%)   66.23        3.95   9.11                                          ______________________________________                                    

EXAMPLE 53

The dye (3.2 parts) of the formula (72) and 80 parts of a 20% solutionof a stilbazole photosensitive resin in polyvinyl alcohol were mixed. Acolor filter substrate with black stripes of 20 μm wide was spin-coatedto a thickness of 3 μm with the resulting mixture. After photomasked,the substrate was exposed to ultraviolet rays under a halogen lamp. Theuncured parts were washed off, whereby a blue filter layer was formed.In a similar manner, red and green filter layers were formed using thecompound (73) and the compound (74), respectively.

The thus-obtained filter for a color LCD was free of color mixingbetween the individual colors and hence had vivid color tones. Inaddition, no quality deterioration was observed although it was heatedto 250° C. during formation of ITO electrodes. The filter did notundergo deterioration either in a weathering test by a weatherometer orin a light-resistance test under carbon arc lamps.

In Table 12, characteristics of the color filter fabricated in Example53 are presented in comparison with those of the color filter fabricatedin Comparative Example 1.

                  TABLE 12                                                        ______________________________________                                                        Example 53                                                                              Comp. Ex. 1                                         Dye migration   Not observed                                                                            Observed                                            ______________________________________                                        Transmittance                                                                 characteristics                                                               Red             A         B                                                   Green           A         B                                                   Blue            A         C                                                   Moistureproofness                                                             Red             A         C                                                   Green           A         B                                                   Blue            A         C                                                   Light resistance                                                              Red             A         B                                                   Green           A         B                                                   Blue            A         C                                                   Heat resistance                                                               Red             A         C                                                   Green           A         B                                                   Blue            A         C                                                   ______________________________________                                    

EXAMPLE 54

Fifteen parts of 1,4-diamino-2,3-dichloroantraquinone, 13 parts ofp-dibutylaminophenol, 8.1 parts of potassium carbonate and 70 parts ofdimethylformamide were reacted at 120° C. for 10 hours. The reactionmixture was poured into 500 parts of 5% hydrochloric acid solution,followed by extraction with 300 parts of chloroform. The extract waspurified by column chromatography (eluent: chloroform-methanol), whereby9 parts of the compound represented by the following formula (75) wereobtained: ##STR109## λmax=521 nm εg=1.7×10⁴ ml/g.cm (solvent: toluene)

Elemental analysis for C₄₂ H₅₂ N₄ O₄ (Mw: 676)

                  TABLE 13                                                        ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            74.56        7.69   8.28                                          Found (%)   74.53        7.75   8.31                                          ______________________________________                                    

EXAMPLE 55

Fifteen parts of the below-described compound having the formula (76)were converted to the acid chloride with thionyl chloride in toluene,followed by reaction with 15 parts of ditolylamine at 90° C. for 4hours. After the reaction mixture was concentrated in an evaporator, theresidue was purified by column chromatography, thereby 10 parts of thecompound represented by the following formula (77) were obtained.##STR110## λmax=509 nm εg=1.4×10⁴ ml/g.cm (solvent: toluene)

Elemental analysis for C₃₇ H₃₀ N₂ O₅ (Mw: 582)

                  TABLE 14                                                        ______________________________________                                                  C          H      N                                                 ______________________________________                                        Calculated (%)                                                                            76.29        5.16   4.81                                          Found (%)   76.31        5.22   4.83                                          ______________________________________                                    

EXAMPLE 56

3 Parts of the dye of formula (75) and 30 parts of "SD-17" (product ofDainippon Ink & Chemicals, Inc.) were mixed. A color filter substratewith black stripes of 20 μm wide was spin-coated to a thickness of 3 μmwith the resulting mixture. After being photomasked, the substrate wasexposed to ultraviolet rays under a halogen lamp. The uncured parts werewashed off, whereby a blue filter layer was formed. In a similar manner,a red filter layer was formed using the compound (77).

The thus-fabricated filter was free of color mixing between theindividual colors and hence had vivid color tones. In addition, noquality deterioration was observed although it was heated to 250° C.during formation of ITO electrodes. The filter did not undergodeterioration either in a weathering test by a weatherometer or in alight-resistance test under carbon arc lamps.

EXAMPLES 57-101

The compounds (D-E-D) shown in Table 15 were synthesized in a similarmanner to Examples 51-52. The compounds (D-B-Z) represented in Table 16were synthesized in a similar manner to Examples 54-55. Each of colorfilters fabricated by using the compounds was free from color mixingbetween the colors and had vivid color tone. In addition, no qualitydeterioration was observed although they were heated to 250° C. duringformation of ITO electrodes. Those filter did not undergo deteriorationeither in a weathering test by a weatherometer or in a light-resistancetest under carbon arc lamps. Incidentally, each λ_(max) was measured intoluene.

                                      TABLE 15                                    __________________________________________________________________________    Compd.                                               λmax              No. D                           E                    (nm)                     __________________________________________________________________________    78                                                                                4 #STR111##                                                                                               7 #STR112##          510                      79                                                                                5 #STR113##                                                                                               8 #STR114##          511                      80                                                                                6 #STR115##                                                                                               9 #STR116##          512                      81                                                                                6 #STR117##                                                                                               0 #STR118##          509                      82                                                                                7 #STR119##                                                                                               1 #STR120##          531                      83                                                                                7 #STR121##                                                                                               2 #STR122##          530                      84                                                                                7 #STR123##                                                                                               3 #STR124##          529                      85                                                                                8 #STR125##                                                                                               4 #STR126##          532                      86                                                                                9 #STR127##                                                                                               5 #STR128##          513                      87                                                                                9 #STR129##                                                                                               6 #STR130##          512                      88                                                                                0 #STR131##                                                                                               7 #STR132##          530                      89                                                                                1 #STR133##                                                                                               8 #STR134##          533                      90                                                                                2 #STR135##                                                                                               9 #STR136##          449                      91                                                                                2 #STR137##                                                                                               0 #STR138##          450                      92                                                                                3 #STR139##                                                                                               1 #STR140##          451                      93                                                                                4 #STR141##                                                                                               2 #STR142##          613                      94                                                                                4 #STR143##                 --CH.sub.2 --        611                      95                                                                                5 #STR144##                                                                                               3 #STR145##          581                      96                                                                                5 #STR146##                                                                                               4 #STR147##          580                      97                                                                                6 #STR148##                                                                                               5 #STR149##          699                      98                                                                                6 #STR150##                 --CH.sub.2 --        698                      __________________________________________________________________________

                                      TABLE 16                                    __________________________________________________________________________    D.paren open-st.B--Z)m                                                        Compd. No.                                                                          D                           B    Z               m λmax          __________________________________________________________________________                                                             (nm)                 99                                                                                  6 #STR151##                 None                                                                               7 #STR152##     1 449                  100                                                                                 7 #STR153##                 --CH.sub.2 --                                                                      8 #STR154##     4 699                  101                                                                                 7 #STR155##                 --CH.sub.2 --                                                                      9 #STR156##     4 698                  102                                                                                 8 #STR157##                 None                                                                               0 #STR158##     4 698                  103                                                                                 9 #STR159##                 --CH.sub.2 --                                                                      1 #STR160##     4 722                  104                                                                                 0 #STR161##                 None                                                                               2 #STR162##     4 720                  105                                                                                 1 #STR163##                 None                                                                               3 #STR164##     4 693                  106                                                                                 2 #STR165##                 --CH.sub.2 --                                                                      1 #STR166##     4 694                  107                                                                                 3 #STR167##                 --CH.sub.2 --                                                                      4 #STR168##     4 710                  108                                                                                 4 #STR169##                 None                                                                               5 #STR170##     2 660                  109                                                                                 5 #STR171##                 None                                                                               6 #STR172##     1 460                  110                                                                                 6 #STR173##                 None                                                                               7 #STR174##     2 543                  111                                                                                 7 #STR175##                                                                                                    8 #STR176##     1 510                  112                                                                                 8 #STR177##                                                                                                    9 #STR178##     1 512                  113                                                                                 9 #STR179##                                                                                                    0 #STR180##     1 510                  114                                                                                 9 #STR181##                 None                                                                               1 #STR182##     1 511                  115                                                                                 0 #STR183##                 None                                                                               2 #STR184##     1 531                  116                                                                                 0 #STR185##                 None                                                                               3 #STR186##     1 530                  117                                                                                 1 #STR187##                 None                                                                               4 #STR188##     1 551                  118                                                                                 2 #STR189##                 None                                                                               5 #STR190##     2 550                  119                                                                                 3 #STR191##                 None                                                                               6 #STR192##     2 549                  120                                                                                 4 #STR193##                 None                                                                               7 #STR194##     1 580                  121                                                                                 5 #STR195##                 None                                                                               8 #STR196##     1 448                  122                                                                                 6 #STR197##                 None                                                                               9 #STR198##     1 447                  __________________________________________________________________________

What is claimed is:
 1. A dye represented by formula (1):

    D-(A-Yn.sup.1)n.sup.2                                      ( 1)

wherein D is a quinophthalone nucleus, A is a connecting group, Y is aphotopolymerizable group represented by any one of formulae (2) to (7)##STR199## wherein R¹ to R⁴ independently represent a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted aralkyl group or a hydrogen atom,R⁵ denotes a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted aralkyl group or a hydrogen atom,R^(5') is a hydrogen atom or methyl group provided that if R^(5') is amethyl group, then R⁵ is a hydrogen atom, and R⁶ to R⁸ independentlymean a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted alkoxylgroup, a halogen atom or a hydrogen atom, _(n) ¹ is 1-10,000, and _(n) ²is an integer from 1 to 10 with the proviso that if Y is formula (4)wherein R⁵ is a hydrogen atom, then D is the quinophthalone nucleusrepresented by the following formula: ##STR200## wherein G is asubstituted or unsubstituted alkyl group.
 2. The dye of claim 1, wherein_(n) ² is an integer from 1-4.
 3. The dye of claim 1, wherein _(n) ¹ and_(n) ² are each
 1. 4. The dye of claim 1, wherein the photopolymerizablegroup represented by Y is selected from the group consisting of thefollowing formulae (2) and (4) to (7) ##STR201## wherein R¹ represents asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedcycloalkyl group, a substituted or unsubstituted aralkyl group or ahydrogen atom, R⁵ denotes a substituted or unsubstituted alkyl group, asubstituted or unsubstituted cycloalkyl group, a substituted orunsubstituted aryl group, a substituted or unsubstituted aralkyl groupor a hydrogen atom, and R⁶ to R⁸ independently mean a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted alkoxyl group,a halogen atom or ahydrogen atom.
 5. A dye formulation adapted for use as a color filtercomprising a dye of claim 1, in admixture with a film forming substratecomprising a photosensitive resin having at least one photopolymerizablesubstituent.
 6. The dye formulation of claim 5, wherein _(n) ² is aninteger from 1-4.
 7. The dye formulation of claim 5, wherein n¹ and _(n)² are each
 1. 8. The dye formulation of claim 5, wherein thephotopolymerizable group represented by Y is selected from the groupconsisting of the following formulae (2), (3), (5), (6) and (7)##STR202## wherein R¹ to R⁴ independently represent a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, a substituted or unsubstituted aralkyl group or a hydrogen atom,and R⁶ to R⁸ independently mean a substituted or unsubstituted alkylgroup, a substituted or unsubstituted cycloalkyl group, a substituted orunsubstituted alkoxyl group,a halogen atom or a hydrogen atom.